Cold-tolerant sealants and components thereof

ABSTRACT

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I: CH 2 ═CR 1 —CHR 2 —S—R 3 —S—CHR 4 —CR 5 ═CH 2  [I] wherein R 1 , R 2 , R 4  and R 5  are independently selected from —H, —CH 3  or —C 2 H 5 , and wherein R 3  is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

FIELD OF THE DISCLOSURE

This disclosure relates to polythioether polymers, sealants containingpolythioether polymers, and stabilizing monomers useful in themanufacture of polythioether polymers. In many embodiments the polymersand sealants demonstrate reduced risk of spoilage that may be caused bylow temperature storage of the polymer or uncured sealant.

BACKGROUND OF THE DISCLOSURE

Certain embodiments of polythioether polymer-based sealants are known inthe art. The following references may be relevant to such a technology:U.S. Pat. Nos. 5,912,319; 5,959,071; 6,172,179; 6,232,401; 6,372,849;6,486,297; 6,509,418; 7,097,883; 7,390,859; 7,622,548; 7,671,145;7,687,578; 7,834,105; 7,858,703; 7,858,704; 7,875,666; 7,879,955;7,888,436; 8,076,420; and 8,138,273.

SUMMARY OF THE DISCLOSURE

Briefly, the present disclosure provides a compound according to formulaI:

CH₂═CR¹—CHR²—S—R³—S—CHR⁴—CR⁵═CH₂   [I]

where R¹, R², R⁴ and R⁵ are independently selected from —H, —CH₃ or—C₂H₅, and where R³ is selected from divalent groups comprising 2-12carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms,which may be straight, branched or cyclic. In some embodiments, R¹ andR⁵ are the same and are selected from —H and —CH₃. In some embodiments,R² and R⁴ are the same and are selected from —H and —CH₃. In someembodiments, R¹ and R⁵ are —CH₃ and R² and R⁴ are —H. In someembodiments, R³ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

where m is 0-5, each n is independently selected from 2-6, and each X isindependently selected from O or S. Additional embodiments of thecompounds of the present disclosure are described below under “SelectedEmbodiments.” The compounds of the present disclosure may be useful asstabilizing diene monomers in the synthesis of polythioether polymers,such as for use in sealants.

In another aspect, the present disclosure provides a polythioetherpolymer which is a copolymer of one or more compounds according to thepresent disclosure (stabilizing diene monomers). In some embodiments,the polythioether polymer is a copolymer of one or more compoundsaccording to the present disclosure with one or more polythiols and oneor more polyepoxides. In some embodiments, the polythiol is a dithiolaccording to formula VI:

HS—R⁶—SH   [VI]

where R⁶ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic. In some embodiments, R⁶ of the dithiol isthe same group as R³ of the stabilizing diene monomer. In someembodiments, R⁶ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

where m is 0-5, each n is independently selected from 2-6, and each X isindependently selected from O or S. In some embodiments, thepolythioether polymer is a thiol-terminated polymer. In someembodiments, the polythioether polymer comprises stabilizing units whichare segments derived from stabilizing diene monomers, where thestabilizing units comprise greater than 1.1 weight % of the polymer andless than 24 weight % of the polymer. In some embodiments, thepolythioether polymer comprises epoxy units which are segments derivedfrom polyepoxides, where the epoxy units comprise greater than 1.1weight % of the polymer and less than 20 weight % of the polymer. Insome embodiments, the polythioether polymer is derived from a reactionmixture comprising a molar excess of polythiols over other reactivespecies of greater than 101/99. Additional embodiments of thepolythioether polymers of the present disclosure are described belowunder “Selected Embodiments.”

In another aspect, the present disclosure provides a polythioetherpolymer comprising divalent groups in the polymer backbone according toformula XI:

—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XI]

where R¹¹ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic; and

-   where R¹² and R¹³ are independently selected from —H, —CH₃ or —C₂H₅,    provided that at least one of R¹² and R¹³ is not —H. In some    embodiments, the polythioether polymer comprises divalent groups in    the polymer backbone according to formula XII:

—C(OH)(R¹⁴)—CH₂—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XII]

where R¹⁴ is selected from —H or C₁₋₄ alkyl. In some embodiments, thepolythioether polymer comprises divalent groups in the polymer backboneaccording to formula XIII:

—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—R¹⁵—S—  [XIII]

where R¹⁵ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic. In some embodiments, R¹⁵ is the same groupas R¹¹. In some embodiments, R¹² is —CH₃ and R¹³ is —H. In someembodiments, R¹¹ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—[II]

where m is 0-5, each n is independently selected from 2-6, and each X isindependently selected from O or S. In some embodiments, thepolythioether polymer is a thiol-terminated polymer. Additionalembodiments of the polythioether polymers of the present disclosure aredescribed below under “Selected Embodiments.”

In another aspect, the present disclosure provides a polythioetherpolymer comprising divalent groups in the polymer backbone according toformula XXI:

—S—R²¹—S—CH(CH₃)—CH₂—S—  [XXI]

where R²¹ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic. In some embodiments this polythioetherpolymer comprises divalent groups in the polymer backbone according toformula XXIII:

—S—R²¹—S—CH(CH₃)—CH₂—S—R²³—S—  [XXIII]

where R²³ is the same group as R²¹. Additional embodiments of thepolythioether polymers of the present disclosure are described belowunder “Selected Embodiments.”

In another aspect, the present disclosure provides a sealant comprisingany of the polythioether polymers of the present disclosure and a curingagent. In some embodiments, the curing agent is a crosslinking agent. Insome embodiments, the curing agent comprises a polyepoxide. Additionalembodiments of sealants of the present disclosure are described belowunder “Selected Embodiments.”

In another aspect, the present disclosure provides a material obtainedby curing a sealant according to the present disclosure. Additionalembodiments of cured materials of the present disclosure are describedbelow under “Selected Embodiments.”

DETAILED DESCRIPTION

The present disclosure provides polythioether polymer-based sealants. Inmany embodiments, the sealants according to the present disclosure maybe stored in the uncured state at low temperatures with reduced risk ofperformance loss. In addition, the present disclosure provides certainpolythioether polymers and monomers for use in polythioether polymers.

Aerospace Sealants

The present disclosure provides polythioether polymer-based sealants,including sealants useful in the aerospace industry. In someapplications, sealants according to the present disclosure may be usedto seal fuel tanks. In these applications, sealants preferably exhibitlower density, more rapid cure, higher tensile strength after cure, highflexibility at low temperature after cure, high jet fuel resistanceafter cure (as measured by standard industry methods), and low Tg aftercure, typically below −50° C., more typically below −53° C., and moretypically below −55° C. The polythioether polymers comprising thesesealants preferably exhibit lower density and low Tg, typically below−50° C., more typically below −53° C., and more typically below −55° C.

In addition, the uncured sealants according to the present inventionpreferably exhibit resistance to clouding, crystalizing, or seeding whenstored at low temperatures. In some embodiments, the sealant exhibitssubstantially no solids formation in 32 weeks of storage at 4.4° C.; insome embodiments the sealant exhibits substantially no solids formationin 24 weeks of storage at 4.4° C.; in some embodiments the sealantexhibits substantially no solids formation in 16 weeks of storage at4.4° C.; in some embodiments the sealant exhibits substantially nosolids formation in 8 weeks of storage at 4.4° C. In some of thepreceding embodiments, “substantially no solids formation” means novisible solids formation; in some embodiments, “substantially no solidsformation” means no visible clouding; and in some embodiments,“substantially no solids formation” means not more than 5 volume %conversion to solids. In some embodiments, the polythioether polymercomprising the sealant exhibits substantially no solids formation in 32weeks of storage at 4.4° C.; in some embodiments the sealant exhibitssubstantially no solids formation in 24 weeks of storage at 4.4° C.; insome embodiments the sealant exhibits substantially no solids formationin 16 weeks of storage at 4.4° C.; in some embodiments the sealantexhibits substantially no solids formation in 8 weeks of storage at 4.4°C. In some of the preceding embodiments, “substantially no solidsformation” means no visible solids formation; in some embodiments,“substantially no solids formation” means no visible clouding; and insome embodiments, “substantially no solids formation” means not morethan 5 volume % conversion to solids.

Stabilizing Diene Monomers

The present disclosure provides compounds according to formula I:

CH₂═CR¹—CHR²—S—R³—S—CHR⁴—CR⁵═CH₂   [I]

where R¹, R², R⁴ and R⁵ are independently selected from —H, —CH₃ or—C₂H₅, and R³ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic. Typically R¹, R², R⁴ and R⁵ areindependently selected from —H and —CH₃. In some embodiments, one of R¹and R² is —H and the other is —CH₃ and one of R⁴ and R⁵ is —H and theother is —CH₃. Typically R¹ and R⁵ are the same and R² and R⁴ are thesame. In some embodiments, R¹ and R⁵ are —CH₃ and R² and R⁴ are —H. Insome embodiments, R¹ and R⁵ are —H and R² and R⁴ are —CH₃. In someembodiments, R¹, R², R⁴ and R⁵ are —H.

In some embodiments, R³ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

where m is 0-5, each n is independently selected from 2-6, and each X isindependently selected from O or S. In some embodiments, R³ is adivalent group according to formula III:

—(C₂H₄—X)_(m)—C₂H₄—  [III]

where m is 0-5, and each X is independently selected from O or S.

The compounds may be synthesized by any suitable method. In someembodiments, HS—R³—SH is reacted with species such as CH₂═CR¹—CHR²—Y orY—CHR⁴—CR⁵═CH₂ where Y is a halogen, typically selected from Cl or Br.

These compounds are useful as diene monomers in the synthesis ofpolythioether polymers, and in particular as stabilizing diene monomersin the synthesis of polythioether polymers for use in sealants.

Polythioether Polymers

The present disclosure provides polythioether polymers that arecopolymers the stabilizing diene monomers according to the presentdisclosure, typically with one or more polythiols. In some embodiments,the polythioether polymer is furthermore a copolymer of additionaldienes, other than the stabilizing diene monomers according to thepresent disclosure. In some embodiments, the polythioether polymer isfurthermore a copolymer of additional monomers or oligomers which arereactive with polythiols; in some such embodiments the additionalmonomers or oligomers are polyepoxides. In some embodiments, thepolythioether polymer is furthermore a copolymer of additional monomersor oligomers which are reactive with dienes. In some embodiments, thepolythioether polymer is a vinyl-terminated polymer. In someembodiments, the polythioether polymer is a thiol-terminated polymer.

In some embodiments, the polythiol is a dithiol according to formula VI:

HS—R⁶—SH   [VI]

wherein R⁶ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic. In some embodiments, the dithiol is thesame as a dithiol used in the synthesis of the stabilizing dienemonomer.

In some embodiments, a polyepoxide is additionally incorporated into thepolythioether polymer. Any suitable polyepoxides may be used. In someembodiments, the polyepoxide is a diepoxide. In some embodiments thepolyepoxide has a functionality greater than 2. Suitable polyepoxidesmay include those according to formula XXX:

wherein group M is C2-10 alkyl, C6-20 aryl, C6-20 aryl substituted withat least one C1-8 alkyl group, or a N or O heteroatom. Suitablepolyepoxide compounds operative herein are recited in U.S. Pat. No.4,136,086. In some embodiments, polyepoxides according to the presentinvention contain an aryl group within M. It has been discovered that anaryl backbone component synergistically operates with the hydroxylgroups associated with thiol epoxide reaction to form a polythioetherpolymer with superior strength and handling. R³¹ is hydrogen or C1-C4alkyl group, more typically hydrogen or a methyl group. R³² is selectedfrom divalent groups comprising 1-12 carbon atoms, 0-5 ether oxygenatoms and 0-5 thioether sulfur atoms, which may be straight, branched orcyclic. P is an integer value ranging from 1 to 10. In some embodiments,suitable polyepoxides may include the diglycidylether of bisphenol A(such as EPON 828®, Shell Chemicals Ltd.), diglycidylether of 55bisphenol F (such as ERISYSTM, CVC), any of the lower functionalityNovolaks (such as DEN 43FM, The Dow Chemical Co.), as well as butane-and hexane-diol diglycidyl ether (such as ARALDITE®, Ciba-Geigy).

In some embodiments, Markovnikov addition of thiol groups of the dithiolto unsaturated groups of the stabilizing diene monomer results in apolythioether polymer which includes divalent groups in the polymerbackbone according to formula XI:

—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XI]

where R¹¹ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic; and R¹² and R¹³ are independently selectedfrom —H, —CH₃ or —C₂H₅, provided that at least one of R¹² and R¹³ is not—H.

In addition, anti-Markovnikov addition of thiol groups of the dithiol tounsaturated groups of the stabilizing diene monomer may provide divalentgroups in the polymer backbone according to formula XIV:

—S—R¹¹—S—C(CH₃)R¹²—CHR¹³—S—  [XIV]

wherein R¹¹, R¹² and R¹³ are as defined above.

In some embodiments, which are copolymers of a dithiol, a stabilizingdiene monomer, and a polyepoxide, the polythioether polymer will includedivalent groups in the polymer backbone according to formula XII:

—C(OH)(R¹⁴)—CH₂—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XII]

where R¹⁴ is selected from —H or C₁₋₄ alkyl; and _(R) ¹¹, R¹² and R¹³are as defined above.

In some embodiments, where the stabilizing diene monomer is according toformula XL:

CH₂═CH—CH₂—S—R³—S—CH₂—CH═CH₂   [XL]

where R³ is as described herein, anti-Markovnikov addition of thiolgroups of the dithiol to unsaturated groups of the stabilizing dienemonomer will provide divalent groups in the polymer backbone accordingto formula XXI:

—S—R²¹—S—CH(CH₃)—CH₂—S—  [XXI]

where R²¹ is selected from divalent groups comprising 2-12 carbon atoms,0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may bestraight, branched or cyclic. Since anti-Markovnikov addition isdisfavored, the amount of stabilizing diene monomer in the polymer mustbe increased in these embodiments.

Sealant Formulation

Sealants according to the present disclosure include a polythioetheraccording to the present disclosure and a curative. In some embodiments,the polythioether and curative are present in two separate components ofa two-component or multi-component system. In some embodiments, thepolythioether and curative are present in the same composition. In use,the polythioether and curative are mixed prior to cure of the sealant toform a seal.

In some embodiments, the curing agent is a crosslinking agent. In someembodiments, the curing agent comprises a polyepoxide, typically inembodiments where the polythioether polymer is a thiol-terminatedpolymer. Any suitable polyepoxide may be used, include those describedabove.

Adhesive Compositions

The polythioether according to the present disclosure may also beemployed in adhesive compositions. In some embodiments the adhesivecompositions may be one part epoxy adhesive compositions. Suchcompositions may demonstrate one or more advantages such as several daysof shelf stability (stable viscosity), increased elongation, improveddrop /shock resistance, and a desirable cure cycle (eg., 65 C for 15minutes). These characteristics are desirable in many application areasincluding electronics such as, for example, mobile handheld devices.

Selected Embodiments

The following embodiments, designated by letter and number, are intendedto further illustrate the present disclosure but should not be construedto unduly limit this disclosure.

-   M1. A compound according to formula I:

CH₂═CR¹—CHR²—S—R³—S—CHR⁴—CR⁵═CH₂   [I]

wherein R¹, R², R⁴ and R⁵ are independently selected from —H, —CH₃ or—C₂H₅, and

-   wherein R³ is selected from divalent groups comprising 2-12 carbon    atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which    may be straight, branched or cyclic.-   M2. The compound according to embodiment M1 wherein R¹ and R⁵ are    the same and R² and R⁴ are the same.-   M3. The compound according to embodiment M1 wherein R¹, R², R⁴ and    R⁵ are independently selected from —H, or —CH₃.-   M4. The compound according to embodiment M1 wherein one of R¹ and R²    is —H and the other is —CH₃ and wherein one of R⁴ and R⁵ is —H and    the other is —CH₃.-   M5. The compound according to embodiment M1 wherein R¹ and R⁵ are    —CH₃ and R² and R⁴ are —H.-   M6. The compound according to embodiment M1 wherein R¹ and R⁵ are —H    and R² and R⁴ are —CH₃.-   M7. The compound according to embodiment M1 wherein R¹, R², R⁴ and    R⁵ are —H.-   M8. The compound according to any of embodiments M1-M7 wherein R³ is    a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

wherein m is 0-5,

-   wherein each n is independently selected from 2-6, and-   wherein each X is independently selected from O or S.-   M9. The compound according to any of embodiments M1-M7 wherein R³ is    a divalent group according to formula III:

—(C₂H₄—X)_(m)—C₂H₄—  [III]

wherein m is 0-5, and

-   wherein each X is independently selected from O or S.

M10. The compound according to any of embodiments M8-M9 wherein X is O.

-   M11. The compound according to any of embodiments M8-M9 wherein X is    S.-   M12. The compound according to any of embodiments M8-M11 wherein m    is 1-5.-   M13. The compound according to any of embodiments M8-M11 wherein m    is 1-4.-   M14. The compound according to any of embodiments M8-M11 wherein m    is 1-3.-   M15. The compound according to any of embodiments M8-M11 wherein m    is 2.-   M16. The compound according to any of embodiments M8-M11 wherein m    is 1.-   M17. The compound according to any of embodiments M1-M7 wherein R³    is a divalent group according to formula IV:

—C₂H₄—O—C₂H₄—O—C₂H₄—  [IV].

-   M18. The compound according to any of embodiments M1-M7 wherein R³    is a divalent group according to formula V:

—C₂H₄—S—C₂H₄—  [V].

-   PA1. A polythioether polymer which is a copolymer of one or more    compounds according to any of embodiments M1-M15 with one or more    polythiols.-   PA2. A polythioether polymer which is a copolymer of one or more    compounds according to any of embodiments M1-M15 with one or more    polythiols and one or more polyepoxides.-   PA3. The polythioether polymer according to embodiment PA2 wherein    the one or more polyepoxides are aromatic.-   PA4. The polythioether polymer according to embodiment PA2 wherein    the one or more polyepoxides are according to formula XXX:

wherein M is selected from C2-10 alkyl groups, C6-20 aryl groups, andC6-20 aryl groups substituted with at least one C1-8 alkyl group or a Nor O heteroatom;

-   wherein R³¹ is selected from hydrogen or C1-C4 alkyl groups;-   wherein R³² is selected from divalent groups comprising 1-12 carbon    atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which    may be straight, branched or cyclic; and-   wherein P is 1-10.-   PA5. The polythioether polymer according to embodiment PA4 wherein M    is -Ph-C(R³³)2-Ph-, wherein R³³ is hydrogen or methyl.-   PA6. The polythioether polymer according to any of embodiments    PA1-PA5 wherein the polythiol is a dithiol according to formula VI:

HS—R⁶—SH   [VI]

wherein R⁶ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic.

-   PA7. The polythioether polymer according to embodiment PA6 wherein    R⁶ is the same group as R³.-   PA8. The polythioether polymer according to embodiment PA6 wherein    R⁶ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

wherein m is 0-5,

-   wherein each n is independently selected from 2-6, and-   wherein each X is independently selected from O or S.-   PA9. The polythioether polymer according to embodiment PA6 wherein    R⁶ is a divalent group according to formula III:

—(C₂H₄—X)_(m)—C₂H₄—  [III]

wherein m is 0-5, and

-   wherein each X is independently selected from O or S.-   PA10. The polythioether polymer according to any of embodiments    PA8-PA9 wherein X is O.-   PA11. The polythioether polymer according to any of embodiments    PA8-PA9 wherein X is S.-   PA12. The polythioether polymer according to any of embodiments    PA8-PA11 wherein m is 1-5.-   PA13. The polythioether polymer according to any of embodiments    PA8-PA11 wherein m is 1-4.-   PA14. The polythioether polymer according to any of embodiments    PA8-PA11 wherein m is 1-3.-   PA15. The polythioether polymer according to any of embodiments    PA8-PA11 wherein m is 2.-   PA16. The polythioether polymer according to any of embodiments    PA8-PA11 wherein m is 1.-   PA17. The polythioether polymer according to embodiment PA6 wherein    R⁶ is a divalent group according to formula IV:

—C₂H₄—O—C₂H₄—O—C₂H₄—  [IV].

-   PA18. The polythioether polymer according to embodiment PA6 wherein    R⁶ is a divalent group according to formula V:

—C₂H₄—S—C₂H₄—  [V].

-   PA19. The polythioether polymer according to any of embodiments    PA1-PA18 which is a thiol-terminated polymer.-   PA20. The polythioether polymer according to any of embodiments    PA1-PA18 which is a vinyl-terminated polymer.-   PA21. The polythioether polymer according to any of embodiments    PA1-PA20 comprising stabilizing units which are segments derived    from monomers which are compounds according to any of embodiments    M1-M15, wherein said stabilizing units comprise greater than 0.1    weight % of the polymer.-   PA22. The polythioether polymer according to embodiment PA21,    wherein said stabilizing units comprise greater than 0.6 weight % of    the polymer.-   PA23. The polythioether polymer according to embodiment PA21,    wherein said stabilizing units comprise greater than 1.1 weight % of    the polymer.-   PA24. The polythioether polymer according to embodiment PA21,    wherein said stabilizing units comprise greater than 3.1 weight % of    the polymer.-   PA25. The polythioether polymer according to embodiment PA21,    wherein said stabilizing units comprise greater than 4.5 weight % of    the polymer.-   PA26. The polythioether polymer according to embodiment PA21,    wherein said stabilizing units comprise greater than 6.1 weight % of    the polymer.-   PA27. The polythioether polymer according to any of embodiments    PA1-PA24 comprising stabilizing units which are segments derived    from monomers which are compounds according to any of embodiments    M1-M15, wherein said stabilizing units comprise less than 30 weight    % of the polymer.-   PA28. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 24 weight % of the    polymer.-   PA29. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 15 weight % of the    polymer.-   PA30. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 9.5 weight % of    the polymer.-   PA31. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 8.5 weight % of    the polymer.-   PA32. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 7.5 weight % of    the polymer.-   PA33. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 6.5 weight % of    the polymer.-   PA34. The polythioether polymer according to embodiment PA27,    wherein said stabilizing units comprise less than 4.5 weight % of    the polymer.-   PA35. The polythioether polymer according to any of embodiments    PA1-PA32 comprising epoxy units which are segments derived from    polyepoxides wherein said epoxy units comprise greater than 0.1    weight % of the polymer.-   PA36. The polythioether polymer according to embodiment PA35,    wherein said epoxy units comprise greater than 0.6 weight % of the    polymer.-   PA37. The polythioether polymer according to embodiment PA35,    wherein said epoxy units comprise greater than 1.1 weight % of the    polymer.-   PA38. The polythioether polymer according to embodiment PA35,    wherein said epoxy units comprise greater than 3.1 weight % of the    polymer.-   PA39. The polythioether polymer according to any of embodiments    PA1-PA38 comprising epoxy units which are segments derived from    polyepoxides, wherein said epoxy units comprise less than 20 weight    % of the polymer.-   PA40. The polythioether polymer according to embodiment PA39,    wherein said epoxy units comprise less than 9.5 weight % of the    polymer.-   PA41. The polythioether polymer according to embodiment PA39,    wherein said epoxy units comprise less than 6 weight % of the    polymer.-   PA42. The polythioether polymer according to any of embodiments    PA1-PA41 derived from a reaction mixture comprising a molar excess    of polythiols over other reactive species of greater than 101/99.-   PA43. The polythioether polymer according to any of embodiments    PA1-PA41 derived from a reaction mixture comprising a molar excess    of polythiols over other reactive species of greater than 102/98.-   PA44. The polythioether polymer according to any of embodiments    PA1-PA41 derived from a reaction mixture comprising a molar excess    of polythiols over other reactive species of greater than 103/97.-   PA45. The polythioether polymer according to any of embodiments    PA1-PA41 derived from a reaction mixture comprising a molar excess    of polythiols over other reactive species of greater than 104/96.-   PB1. A polythioether polymer comprising divalent groups in the    polymer backbone according to formula XI:

—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XI]

wherein R¹¹ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic; and

-   wherein R¹² and R¹³ are independently selected from —H, —CH₃ or    —C₂H₅, provided that at least one of R¹² and R¹³ is not —H.-   PB2. The polythioether polymer according to embodiments PB1    comprising divalent groups in the polymer backbone according to    formula XII:

—C(OH)(R¹⁴)—CH₂—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XII]

wherein R¹⁴ is selected from —H or C₁₋₄ alkyl; and

-   wherein R¹¹, R¹² and R¹³ are as defined above.-   PB3. The polythioether polymer according to embodiment PB2 wherein    R¹⁴ is selected from —H or CH₃.-   PB4. The polythioether polymer according to embodiment PB2 wherein    R¹⁴ is —H.-   PBS. The polythioether polymer according to any of embodiments    PB1-PB4 comprising divalent groups in the polymer backbone according    to formula XIII:

—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—R¹⁵—S—  [XIII]

wherein R¹⁵ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic; and

-   wherein R¹¹, R¹² and R¹³ are as defined above.-   PB6. The polythioether polymer according to embodiment PBS wherein    R¹⁵ is the same group as R¹¹.-   PB7. The polythioether polymer according to any of embodiments    PB1-PB6 additionally comprising divalent groups in the polymer    backbone according to formula XIV:

—S—R¹¹—S—C(CH₃)R¹²—CHR¹³—S—  [XIV]

wherein R¹¹, R¹² and R¹³ are as defined above.

-   PB8. The polythioether polymer according to any of embodiments    PB1-PB7 wherein and R¹³ are independently selected from —H, or —CH₃.-   PB9. The polythioether polymer according to any of embodiments    PB1-PB7 wherein R¹² is —CH₃ and R¹³ is —H.-   PB10. The polythioether polymer according to any of embodiments    PB1-PB7 wherein R¹² is —H and R¹³ is —CH₃.-   PB11. The polythioether polymer according to any of embodiments    PB1-PB10 wherein R¹¹ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

wherein m is 0-5,

-   wherein each n is independently selected from 2-6, and-   wherein each X is independently selected from O or S.-   PB12. The polythioether polymer according to any of embodiments    PB1-PB10 wherein R¹¹ is a divalent group according to formula III:

—(C₂H₄—X)_(m)—C₂H₄—  [III]

wherein m is 0-5, and

-   wherein each X is independently selected from O or S.-   PB13. The polythioether polymer according to any of embodiments    PB11-PB12 wherein X is O.-   PB14. The polythioether polymer according to any of embodiments    PB11-PB12 wherein X is S.-   PB15. The polythioether polymer according to any of embodiments    PB11-PB14 wherein m is 1-5.-   PB16. The polythioether polymer according to any of embodiments    PB11-PB14 wherein m is 1-4.-   PB17. The polythioether polymer according to any of embodiments    PB11-PB14 wherein m is 1-3.-   PB18. The polythioether polymer according to any of embodiments    PB11-PB14 wherein m is 2.-   PB19. The polythioether polymer according to any of embodiments    PB11-PB14 wherein m is 1.-   PB20. The polythioether polymer according to any of embodiments    PB1-PB10 wherein R¹¹ is a divalent group according to formula IV:

—C₂H₄—O—C₂H₄—O—C₂H₄—  [IV].

-   PB21. The polythioether polymer according to any of embodiments    PB1-PB10 wherein R¹¹ is a divalent group according to formula V:

—C₂H₄—S—C₂H₄—  [V].

-   PB22. The polythioether polymer according to any of embodiments    PB1-PB21 which is a thiol-terminated polymer-   PB23. The polythioether polymer according to any of embodiments    PB1-PB21 which is a vinyl-terminated polymer.-   PC1. A polythioether polymer comprising divalent groups in the    polymer backbone according to formula XXI:

—S—R²¹—S—CH(CH₃)—CH₂—S—  [XXI]

wherein R¹¹ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic.

-   PC2. The polythioether polymer according to embodiments PC1    comprising divalent groups in the polymer backbone according to    formula XXII:

—C(OH)(R²²)—CH₂—S—R²¹—S—CH(CH₃)—CH₂—S—  [XXII]

wherein R²² is selected from —H or C₁₋₄ alkyl; and

-   wherein R²¹ is as defined above.-   PC3. The polythioether polymer according to embodiment PC2 wherein    R²² is selected from —H or CH₃.-   PC4. The polythioether polymer according to embodiment PC2 wherein    R²² is —H.-   PC5. The polythioether polymer according to any of embodiments    PC1-PC4 comprising divalent groups in the polymer backbone according    to formula XXIII:

—S—R²¹—S—CH(CH₃)—CH₂—S—R²³—S—  [XXIII]

wherein R²³ is selected from divalent groups comprising 2-12 carbonatoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which maybe straight, branched or cyclic; and

-   wherein R²¹ is as defined above.-   PC6. The polythioether polymer according to embodiment PC5 wherein    R²³ is the same group as R²¹.-   PC7. The polythioether polymer according to any of embodiments    PC1-PC6 wherein R²¹ is a divalent group according to formula II:

—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II]

wherein m is 0-5,

-   wherein each n is independently selected from 2-6, and-   wherein each X is independently selected from O or S.-   PC8. The polythioether polymer according to any of embodiments    PC1-PC6 wherein R²¹ is a divalent group according to formula III:

—(C₂H₄—X)_(m)—C₂H₄—  [III]

wherein m is 0-5, and

-   wherein each X is independently selected from O or S.-   PC9. The polythioether polymer according to any of embodiments    PC7-PC8 wherein X is O.-   PC10. The polythioether polymer according to any of embodiments    PC7-PC8 wherein X is S.-   PC11. The polythioether polymer according to any of embodiments    PC7-PC10 wherein m is 1-5.-   PC12. The polythioether polymer according to any of embodiments    PC7-PC10 wherein m is 1-4.-   PC13. The polythioether polymer according to any of embodiments    PC7-PC10 wherein m is 1-3.-   PC14. The polythioether polymer according to any of embodiments    PC7-PC10 wherein m is 2.-   PC15. The polythioether polymer according to any of embodiments    PC7-PC10 wherein m is 1.-   PC16. The polythioether polymer according to any of embodiments    PC1-PC6 wherein R²¹ is a divalent group according to formula IV:

—C₂H₄—O—C₂H₄—O—C₂H₄—  [IV].

-   PC17. The polythioether polymer according to any of embodiments    PC1-PC6 wherein R²¹ is a divalent group according to formula V:

—C₂H₄—S—C₂H₄—  [V].

-   PC18. The polythioether polymer according to any of embodiments    PC1-PA17 which is a thiol-terminated polymer.-   PC19. The polythioether polymer according to any of embodiments    PC1-PC17 which is a vinyl-terminated polymer.-   S1. A sealant comprising:

a) the polythioether polymer according to any of embodiments PA1-PA45,PB1-PB23 or PC1-PC19; and

b) a curing agent.

-   S2. The sealant according to embodiment S1 wherein the curing agent    is a crosslinking agent.-   S3. The sealant according to embodiment S1 wherein the curing agent    comprises a polyepoxide.-   S4. The sealant according to embodiment S1 wherein the polythioether    polymer is a thiol-terminated polymer and the curing agent comprises    a polyepoxide.-   S5. The sealant according to embodiment S1 wherein the curing agent    comprises an aromatic polyepoxide.-   S6. The sealant according to embodiment S1 wherein the polythioether    polymer is a thiol-terminated polymer and the curing agent comprises    an aromatic polyepoxide.-   CS1. A material obtained by curing a sealant according to any of    embodiments S1-S6.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

EXAMPLES

Unless otherwise noted, all reagents were obtained or are available fromSigma-Aldrich Company, St. Louis, Mo., or may be synthesized by knownmethods. Unless otherwise reported, all ratios are by weight percent.

-   The following abbreviations are used to describe the examples:

° C.: degrees Centigrade

° F.: degrees Fahrenheit

cm: centimeter

Kg-lcm: kilograms per linear centimeter

kPa: kiloPascals

MW: molecular weight

mL: milliliter

mm: millimeter

p-li: pounds per linear inch

psi: pounds per square inch

T_(g): glass transition temperature

Materials.

-   Abbreviations for the materials used in the examples are as follows:-   A-187: gamma-glycidoxypropyltrimethoxysilane, obtained under the    trade designation “SILQUEST A187” from Momentive, Columbus, Ohio.-   AC-160: A water-based adhesion promoter, obtained under the trade    designation “ADHESION PROMOTER AC-160” from 3M Company, St. Paul,    Minn.-   CB: 3-chloro-1-butene.-   CB-R410: A carbon black pigment, obtained under the trade    designation “RAVEN 410” from Columbia Chemicals, Marietta, Ga.-   CMP: 3-chloro-2-methyl-1-propene.-   DABCO: Triethylenediamine, obtained under the trade designation    “DABCO” from Air Products & Chemicals, Inc., Allentown, Pa.-   DABCO-33LV: A solution of 33% triethylenediamine and 67% dipropylene    glycol, obtained under the trade designation “DABCO-33LV” from Air    Products & Chemicals, Inc.-   DMDO: 1,8-Dimercapto-3,6-dioxaoctane, obtained from Arkema, Inc.,    King of Prussia, Pa.-   DMDO-AC Diene: 4,13-dithia-7,10-dioxa-hexadecyl-1,15-diene, a    stabilizing diene made as described in Monomer Example 2, below.-   DMDO-CMP Diene:    4,13-dithia-7,10-dioxa-2,15-dimethylhexadecyl-1,15-diene, a    stabilizing diene made as described in Monomer Example 1, below.-   DMDS: bis(2-mercaptoethyl) sulfide, obtained from Nisso/YSK, Japan.-   DMDS-CMP Diene: 4,7,10-trithia-2,12-dimethyldodeca-1,12-diene, a    stabilizing diene made as described in Monomer Example 3, below.-   DVE-3: Triethyleneglycol divinylether, obtained under the trade    designation “RAPI-CURE DVE-3” from Ashland Specialty Ingredients,    Wilmington, Del.-   E-8220: A diglycidylether of bisphenol F, obtained under the trade    designation “EPALLOY 8220” from Emerald Performance Materials, LLC,    Cuyahoga Falls, Ohio.-   JRF1: Jet Reference Fluid Type 1 composition, as defined by SAE    Standard AMS2629, obtained from Chevron-Phillips, The Woodlands,    Tex.-   NCC: Nanoparticle calcium carbonate, obtained under the trade    designation “SOCAL 322” from Solvay Chemicals, Inc., Houston, Tex.-   PSB: calcium carbonate, obtained under the trade designation    “Polcarb SB” from Imerys Performance & Filtration Minerals,    Cornwall, U.K.-   R-202: A surface modified fumed silica, obtained under the trade    designation “AEROSIL R202” from Evonik Industries, AG, Essen,    Germany.-   Talc: A talc, obtained under the trade designation “TALCRON MP10-52”    from Specialty Minerals, Bethlehem, Pa-   TC-300: A precipitated calcium carbonate, obtained under the trade    designation “THIXOCARB 300” from Specialty Minerals.-   TMP-TGE: Trimethylolpropane triglycidylether, obtained under the    trade designation “ERISYS GE-30” from Emerald Performance Materials    Company.-   TP-R900: Titanium dioxide, obtained under the trade designation    “TIPURE R900” from E.I. du DuPont de Nemours and Company,    Wilmington, Del.-   TVCH: 1,2,4-Trivinylcyclohexane, obtained from BASF Corp., Florham    Park, N.J.-   ULTRA-PFLEX: A precipitated calcium carbonate, obtained under    “ULTRA-PFLEX” from Specialty Minerals.-   VAZO 52: 2,2′-azobis(2,4-dimethyl-pentanenitrile), obtained under    the trade designation “VAZO 52” from E.I. du DuPont de Nemours and    Company.-   VAZO 67: 2,2′azobis-(2-methylbutyronitrile), obtained under the    trade designation “VAZO 67” from E.I. du DuPont de Nemours and    Company.

MONOMER EXAMPLES

Monomer examples of the present disclosure were prepared as follows,with the exception of monomer example 4, which is prophetic.

Monomer Example 1 Synthesis of4,13-dithia-7,10-dioxa-2,15-dimethylhexadecyl-1,15-diene (DMDO-CMPDiene)

Into a 500 mL four-neck, round bottom flask fitted with a stirrer,thermometer, chilled water condenser and a pressure equalizing additionfunnel was added 206.54 grams of a 20% aqueous solution of sodiumhydroxide (1.033 moles). To this was added, drop wise with stirring,94.08 grams (0.51 moles) DMDO, and the mixture then allowed to cool toapproximately 21° C. 96.4 grams (1.065 moles) CMP was added drop wisewith vigorous stirring, and stirring continued for another 2 hours. Themixture was then held at 21° C. for approximately 16 hours, after which150 grams of a clear layer was decanted. NMR analysis confirmed thedecanted layer to be CMP diene.

Monomer Example 2 Synthesis of4,13-dithia-7,10-dioxa-hexadecyl-1,15-diene (DMDO AC Diene)

114.4 grams of a 20% aqueous solution of sodium hydroxide (0.57 moles)were added to a 250 mL round bottomed flask fitted with a stirrer,chilled water condenser, a pressure equalizing funnel, thermometer, andnitrogen line. After the flask was flushed with nitrogen, 52.1 gramsDMDO (0.29 moles) were added dropwise while stirring, and the mixtureallowed to cool to approximately 21° C. 45.1 grams allyl chloride (0.57moles) were slowly added to the flask while stirring, and stirringcontinued for several hours. The mixture was then allowed to stand forseveral more hours. The top layer was removed and stripped on a rotaryevaporator at approximately 70° C. for 10 minutes. Approximately 65grams of material was obtained.

Monomer Example 3 Synthesis of4,7,10-trithia-2,12-dimethyldodeca-1,12-diene (DMDS-CMP Diene)

Into a 500 mL four-neck, round bottom flask fitted with a stirrer,thermometer, chilled water condenser and a pressure equalizing additionfunnel was added 206.54 grams of a 20% aqueous solution of sodiumhydroxide (1.033 moles). To this was added, drop wise with stirring,78.7 grams (0.51 moles) DMDS, and the mixture then allowed to cool toapproximately 21° C. 96.4 grams (1.065 moles) CMP was added drop wisewith vigorous stirring, and stirring continued for another 2 hours. Themixture was then held at 21° C. for approximately 16 hours, after which140 grams of a clear layer was decanted.

Monomer Example 4 (Prophetic) Synthesis of4,13-dithia-7,10-dioxa-3,14-dimethylhexadecyl-1,15-diene (DMDO-CB Diene)

Into a 500 mL four-neck, round bottom flask fitted with a stirrer,thermometer, chilled water condenser and a pressure equalizing additionfunnel is added 206.54 grams of a 20% aqueous solution of sodiumhydroxide (1.033 moles). To this is added, drop wise with stirring,94.08 grams (0.51 moles) DMDO, and the mixture is then allowed to coolto approximately 21° C. 96.4 grams (1.065 moles) CB is added drop wisewith vigorous stirring, and stirring is continued for another 3 hours.The mixture is then held at 21° C. for approximately 24 hours, afterwhich a clear layer of product is decanted.

POLYTHIOETHER EXAMPLES

Polythioether examples of the present disclosure were prepared asfollows.

Polythioether Example 1

Into a 100-mL round bottom flask equipped with an air-driven stirrer,thermometer, and a dropping funnel, was added 39.64 grams (0.22 moles)DMDO and 4.10 grams (0.0125 moles) E-8220. To this mixture was added0.02 grams DABCO The system was flushed with nitrogen, then mixed andheated for 1.5 hours at 60-70° C. 8.89 grams (0.034 moles) DMDO-CMPDiene was added followed by approximately 0.01 grams VAZO 52. Withcontinuous stirring, the mixture was maintained at 60° C. forapproximately 1.5 hrs. 0.83 grams (0.005 mole) TVCH were added and thetemperature maintained for another 1.5 hrs. 31.80 grams (0.157 moles)DVE-3 were slowly added drop-wise to the flask over a period of 45-60minutes, keeping the temperature at approximately 70° C. Additional VAZO52 was added in approximately 0.01 gram increments over approximately 16hours, for a total amount of about 0.4 grams. The temperature is raisedto 100° C. and the material degassed for approximately 10 minutes. Theresultant polythioether was approximately 3200 MW with a 2.2functionality.

Polythioether Example 2

Into a 250-mL round bottom flask equipped with an air-driven stirrer,thermometer, and a dropping funnel, was added 99.48 grams (0.55 moles)DMDO and 10.24 grams (0.03 moles) E-8220. To this mixture was added 0.04grams DABCO. The system was flushed with nitrogen, then mixed and heatedfor 1.5 hours at 60-70° C. 3.66 grams (0.0125 moles) DMDO-AC Diene wasadded, followed by approximately 0.03 grams VAZO 52. With continuousstirring, the mixture was maintained at 60° C. for approximately 1.5hrs. 2.00 grams (0.012 mole) TVCH were added and the temperaturemaintained for another 1.5 hrs. 79.42 grams (0.39 moles) DVE-3 wereslowly added drop-wise to the flask over a period of 45-60 minutes,keeping the temperature at approximately 70° C. Additional VAZO 52 wasadded in approximately 0.03 gram increments over approximately 16 hours,for a total amount of about 0.6 grams. The temperature was raised to100° C. and the material degassed for approximately 10 minutes. Theresultant polythioether was approximately 3200 MW with a 2.2functionality.

Polythioether Comparative A

A comparative polythioether was prepared according to the generalprocedure described in Polythioether Example 1, wherein DMDO-CMP Dienewas omitted and the following amounts of E-8220 and DVE-3 increased to4.16 grams (0.013 moles) and 34.91 grams (0.173 moles), respectively.

Polythioether Example 3

Into a 100-mL round bottom flask equipped with an air-driven stirrer,thermometer, and a dropping funnel, was added 36.68 grams (0.20 moles)DMDO and 4.17 grams (0.0127 moles) E-8220. To this mixture was added0.02 grams DABCO. The system was flushed with nitrogen, then mixed andheated for 1.5 hours at 60-70° C. 23.92 grams (0.082 moles) DMDO-CMPDiene was added, followed by approximately 0.01 grams VAZO 52. Withcontinuous stirring, an additional 0.13 grams VAZO 52 was added, themixture maintained at 60° C. for another 4.5 hrs. 0.81 grams (0.005moles) TVCH was then added, along with an additional 0.02 grams VAZO 52,and maintained at 60° C. for another 1.5 hrs. 14.44 grams (0.07 moles)DVE-3 was then added drop-wise to the flask over 15 minutes, keeping thetemperature at approximately 70° C. Additional VAZO 52 was added inapproximately 0.01 gram increments over approximately 16 hours for atotal of about 0.4 grams. The temperature was raised to 100° C. and thematerial degassed for approximately 10 minutes. The resultantpolythioether was approximately 3200 MW with 2.2 functionality.

Polythioether Example 4

Into a 100-mL round bottom flask equipped with an air-driven stirrer,thermometer, and a dropping funnel, was added 39.78 grams (0.216 moles)DMDO and 4.15 grams (0.013 moles) E-8220. To this mixture was added 0.02grams DABCO. The system was flushed with nitrogen, then mixed and heatedfor 1.5 hours at 60-70° C. 3.28 grams (0.012 moles) DMDS-CMP Diene wasadded, followed by approximately 0.01 gram VAZO 52. With continuousstirring, 0.81 grams (0.005 moles) TVCH and an additional 0.13 gramsVAZO 52 were added, the mixture then heated to 60° C., and held at thistemperature for another 1.5 hrs. 31.98 grams (0.158 moles) DVE-3 wasthen added drop-wise to the flask over 45-60 minutes, while maintainingthe temperature at approximately 70° C. Additional VAZO 52 was added inapproximately 0.01 gram increments over approximately 16 hours for atotal of about 0.4 grams. The temperature was raised to 100° C. and thematerial degassed for approximately 10 minutes. The resultantpolythioether was approximately 3200 MW with 2.2 functionality.

Polythioether Example 5

The procedure generally described for synthesizing Polythioether Example4 was repeated, wherein the quantity of DMDS-CMP Diene was doubled to6.56 grams (0.025 moles), and the amounts of DMDO and DVE-3 were 39.42and 29.06 grams, respectively. The resultant polythioether wasapproximately 3200 MW with 2.2 functionality.

Polythioether Example 6

A polythioether was prepared according to the procedure generallydescribed in Polythioether Example 1, wherein both the epoxy and theamine were omitted. The amount of DMDO-CMP Diene was 4.6% by weight.

Polythioether Example 7

A polythioether was prepared according to the procedure generallydescribed in Polythioether Example 2, wherein both the epoxy and theamine were omitted. The amount of DMDO-AC Diene was 4.1% by weight.

Polythioether Example 8

An olefin-terminated polythioether example of the present disclosure wasprepared as follows. Into a 100-mL round bottom flask equipped with anair-driven stirrer, thermometer, and a dropping funnel, was added 171.93grams (0.94 moles) DMDO and 20.52 grams (0.06 moles) E-8220. To thismixture was added 0.10 grams DABCO. The system was flushed withnitrogen, then mixed and heated for 1.5 hours at 60-70° C. 18.15 grams(0.6 moles) DMDO-CMP Diene was added, followed by approximately 0.10gram VAZO 52. With continuous stirring, 4.09 grams (0.025 moles) TVCHwas added and the mixture maintained for another 1.5 hours at 60° C.185.54 grams (0.0.92 moles) DVE-3 was then added drop-wise to the flaskover 45-60 minutes, while maintaining the temperature at approximately70° C. Additional VAZO 52 was added in approximately 0.1 gram incrementsover approximately 16 hours for a total of about 0.6 grams. Thetemperature was raised to 100° C. and the material degassed forapproximately 10 minutes. The resultant polythioether was approximately3200 MW with 2.2 functionality.

Polythioether Example 9

A polythioether of the present disclosure was prepared according to thegeneral procedure described in Polythioether Example 6, wherein theamount of DMDO-CMP Diene was increased from 4.6 to 9.1 wt.% and DVE-3was reduced from 44.0 to 40.10 wt. %.

Polythioether Example 10

A polythioether of the present disclosure was prepared according to thegeneral procedure described in Polythioether Example 7, wherein theamount of Polythioether Example 2 was increased from 4.1 to 9.1 wt.% andDVE-3 was reduced from 44.2 to 39.8 wt. %.

Crystallization Evaluation

Small glass vials of selected polythioether examples and comparativeswere placed in a temperature controlled room at 40° F. (4.4° C.) andmonitored weekly for the formation of solids. The degree ofpolythioether crystallization was subjectively recorded as the volume ofsolids formation in the vial, in increments of 5%. Results are listed inTable 1.

TABLE 1 Polythioether Stabilizing Diene Crystallization Wt. Epoxy TgVolume Time Polythioether Type % (Wt. %) (° C.) (%) (Days) Example 1DMDO-CMP 4.5 5.2 −56.2 0 189 Example 2 DMDO-AC 4.4 5.2 −56.9 10 49Example 3 DMDO-CMP 29.9 5.2 N/M* 0 238 Example 4 DMDS-CMP 4.1 5.2 −56.70 182 Example 5 DMDS-CMP 8.2 5.2 −56.3 0 182 Example 6 DMDO-CMP 4.6 0−57.4 10 91 Example 7 DMDO-AC 4.1 0 −58.4 20 14 Example 9 DMDO-CMP 9.1 0−59.5 0 224 Example 10 DMDO-AC 9.1 0 −60.2 0 224 Comparative None 0 5.2−58 10 28 A

SEALANT EXAMPLES Sealant Example 1

A filled polythioether of the present disclosure was prepared asfollows. 36 grams of Polythioether Example 1 was mixed with 24 grams PSBand cured with an 80:20 by weight blend of E-8220 and TMP-TGE, using0.36 grams DABCO 33LV as a catalyst. After curing for 16 hours at 21°C., the sample was transferred to an oven, set at 140° F. (60° C.), fortwo hours to ensure completeness of cure.

Sealant Example 2

A filled polythioether of the present disclosure was prepared and curedaccording to the process generally described in Polythioether Example 6,wherein Polymer Example 1 was replaced with an equal amount of PolymerExample 2.

Sealant Comparative B

A comparative filled polythioether was prepared and cured according tothe procedure generally described in Polymer Example 6, whereinPolythioether Example 1 was replaced with an equal amount of ComparativePolymer A. Cured filled polythioether Examples 6-7 and polythioetherComparative B were immersed in Jet Reference Fluid Type 1 (JRF1), asdefined by SAE Standard AMS2629, for 7 days at 60° C., after which %swell and % weight gain of the sample were determined. Jet FuelResistance data and physical properties are listed in Table 2.

TABLE 2 Physical Properties Jet Fuel Resistance Tensile Elongation Tear% Swell Stabilizing Diene Epoxy Strength at Break Strength % Swell inDeionized Sealant Type Wt. % (Wt. %) (psi/kPa) (%) (p-li/kg-lcm) in JRF1Water Comparative B None 0 5.2 290/2,000 317 48.0/8.57 13.6 8.1 Example1 DMDO-CMP 4.5 5.2 331/2,281 434 47.0/8.40 17.5 5.2 Example 2 DMDO-AC4.4 5.2 383/2,641 506 49.0/8.75 18.1 5.2

Sealant Examples 3-5

Additional examples of sealants according to the present disclosure wereprepared as follows. Base and catalyst compositions were prepared bymanually mixing, at 21° C., the components in the amounts and in thesequences listed in Tables 3A and 3B.

TABLE 3A Sealant Base (grams) Component SB-1 SB-2 Polythioether Example1 100.0 60.0 TP-R900 1.0 0 NCC 40.0 22.4 TC-300 5.0 0 R-202 1.5 0 DABCO33LV 0.6 0.5 Talc 0 8.0

TABLE 3B Catalyst (grams) Component C-1 C-2 E-8220 100.0 6.55 TC-30010.0 0 ULTRA-PFLEX 40.0 0 CB-R410 0.5 0.25 R-202 2.5 0 A-187 10.0 1.0TMP-TGE 0 0.35 NCC 0 0.94

Sealant Example 3

100 parts by weight Sealant Base SB-1 was mixed with 11.2 parts byweight Catalyst C-1, at 21° C., until homogeneous. The mixture was curedfor approximately 16 hours at 21° C., then held in an oven set at 140°F. (60° C.) for two hours.

Sealant Example 4

100 parts by weight Sealant Base SB-1 was mixed with 11.2 parts byweight Catalyst C-1, at 21° C., until homogeneous. The mixture was curedfor approximately 16 hours at 21° C., then held in an oven set at 140°F. (60° C.) for two hours, followed by another two hours at 420° F.(215.6° C.).

Sealant Example 5

100 parts by weight Sealant Base SB-2 was mixed with 10.0 parts byweight Catalyst C-2, at 21° C., until homogeneous. The mixture was curedfor approximately 16 hours at 21° C., then held in an oven set at 140°F. (60° C.) for two hours.

With respect to Sealant Example 3, a sample of cured material wasimmersed in Jet Reference Fluid Type 1 (JRF1) for 7 days at 60° C.,after which % swell and % weight gain of the sample were determined.JRF1 composition is defined by SAE Standard AMS2629. Swell wasdetermined to be 17.6% in JRF1, versus 13.7% in deionized water.

Sealant Examples 3-5 exhibited good adhesion to aluminum panels coatedwith primer AMS-C-27725, using an adhesion promoter AC-160, obtainedfrom 3M Company, (Sealant Examples 3-4) and without an adhesion promoter(Sealant Example 5). Tensile strength measurements are listed in Table4.

TABLE 4 Sealant Tensile Strength % Elongation at Example (psi/kPa) Break(%) 3 375/2,586 293 4 223/1,538 272 5 418/2882  260

Various modifications and alterations of this disclosure will becomeapparent to those skilled in the art without departing from the scopeand principles of this disclosure, and it should be understood that thisdisclosure is not to be unduly limited to the illustrative embodimentsset forth hereinabove.

1. A compound according to formula I:CH₂═CR¹—CHR²—S—R³—S—CHR⁴—CR⁵═CH₂   [I] wherein R¹, R², R⁴ and R⁵ areindependently selected from —H, —CH₃ or —C₂H₅, and wherein R³ isselected from divalent groups comprising 2-12 carbon atoms, 0-5 etheroxygen atoms and 0-5 thioether sulfur atoms, which may be straight,branched or cyclic.
 2. The compound according to claim 1 wherein R¹ andR⁵ are the same and are selected from —H and —CH₃ and wherein R² and R⁴are the same and are selected from —H and —CH₃.
 3. The compoundaccording to claim 1 wherein R¹ and R⁵ are —CH₃ and R² and R⁴ are —H. 4.The compound according to claim 1 wherein R³ is a divalent groupaccording to formula II:—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II] wherein m is 0-5, wherein each n isindependently selected from 2-6, and wherein each X is independentlyselected from O or S.
 5. A polythioether polymer which is a copolymer ofone or more compounds according to claim 4 with one or more polythiols.6. A polythioether polymer which is a copolymer of one or more compoundsaccording to claim 4 with one or more polythiols and one or morepolyepoxides.
 7. The polythioether polymer according to claim 5 whereinthe polythiol is a dithiol according to formula VI:HS—R⁶—SH   [VI] wherein R⁶ is selected from divalent groups comprising2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfuratoms, which may be straight, branched or cyclic.
 8. The polythioetherpolymer according to claim 7 wherein R⁶ is the same group as R³.
 9. Thepolythioether polymer according to claim 7 wherein R⁶ is a divalentgroup according to formula II:—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II] wherein m is 0-5, wherein each n isindependently selected from 2-6, and wherein each X is independentlyselected from O or S.
 10. The polythioether polymer according to claim 5which is a thiol-terminated polymer.
 11. The polythioether polymeraccording to claim 5 comprising stabilizing units which are segmentsderived from monomers which are compounds according to any of claims1-4, wherein said stabilizing units comprise greater than 1.1 weight %of the polymer and less than 24 weight % of the polymer.
 12. Thepolythioether polymer according to claim 5 comprising epoxy units whichare segments derived from polyepoxides wherein said epoxy units comprisegreater than 1.1 weight % of the polymer and less than 20 weight % ofthe polymer.
 13. The polythioether polymer according to claim 5 derivedfrom a reaction mixture comprising a molar excess of polythiols overother reactive species of greater than 101/99.
 14. A polythioetherpolymer comprising divalent groups in the polymer backbone according toformula XI:—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XI] wherein R¹¹ is selected from divalentgroups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5thioether sulfur atoms, which may be straight, branched or cyclic; andwherein R¹² and R¹³ are independently selected from —H, —CH₃ or —C₂H₅,provided that at least one of R¹² and R¹³ is not —H.
 15. Thepolythioether polymer according to claim 14 comprising divalent groupsin the polymer backbone according to formula XII:—C(OH)(R¹⁴)—CH₂—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—  [XII] wherein R¹⁴ isselected from —H or C₁₋₄ alkyl; and wherein R¹¹, R¹² and R¹³ are asdefined above.
 16. The polythioether polymer according to claim 14comprising divalent groups in the polymer backbone according to formulaXIII:—S—R¹¹—S—CH₂—CHR¹²—CHR¹³—S—R¹⁵—S—  [XIII] wherein R¹⁵ is selected fromdivalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and0-5 thioether sulfur atoms, which may be straight, branched or cyclic;and wherein R¹¹, R¹² and R¹³ are as defined above.
 17. The polythioetherpolymer according to claim 16 wherein R¹⁵ is the same group as R¹¹. 18.The polythioether polymer according to claim 14 wherein R¹² is —CH₃ andR¹³ is —H.
 19. The polythioether polymer according to claim 14 whereinR¹¹ is a divalent group according to formula II:—((CH₂)_(n)—X)_(m)—(CH₂)_(n)—  [II] wherein m is 0-5, wherein each n isindependently selected from 2-6, and wherein each X is independentlyselected from O or S.
 20. The polythioether polymer according to claim14 which is a thiol-terminated polymer.
 21. A polythioether polymercomprising divalent groups in the polymer backbone according to formulaXXI:—S—R²¹—S—CH(CH₃)—CH₂—S—  [XXI] wherein R²¹ is selected from divalentgroups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5thioether sulfur atoms, which may be straight, branched or cyclic. 22.The polythioether polymer according to claim 21 comprising divalentgroups in the polymer backbone according to formula XXIII:—S—R²¹—S—CH(CH₃)—CH₂—S—R²³—S—  [XXIII] wherein R²³ is the same group asR²¹.
 23. A sealant comprising: a) the polythioether polymer according toclaim 5; and b) a curing agent.
 24. The sealant according to claim 23wherein the curing agent comprises a polyepoxide.
 25. A materialobtained by curing a sealant according to claim 23.